Silicone polymerisates

ABSTRACT

Silicone-containing polymers having numerous uses are prepared by polymerizing one or more ethylenically unsaturated monomers in the presence of a branched organopolysiloxane having at least one lipophilic branched siloxane portion and at least one optionally branched hydrophilic portion.

The invention relates to silicone-containing polymers, a process forproducing them and their use.

Organosilicon compounds such as organosiloxane polymers are used forhydrophobicizing polymers of ethylenically unsaturated monomers. Suchhydrophobically modified polymers are used in many fields in the form oftheir polymer powders, in particular water-redispersible polymerpowders, or as aqueous polymer dispersions. They are employed as bindersin coating compositions or adhesives, in particular in the buildingsector and textile sector, and as binders in cosmetics and hair carecompositions.

It is known from WO-A 95/20626 that water-redispersible polymer powderscan be modified by addition of noncopolymerizable organosiliconcompounds. EP-A 0352339 describes protective paints for concreteconstructions, which comprise copolymers of divinyl-polydimethylsiloxanewith acrylate or methacrylate esters and vinyl- or acryl-functionalalkoxysilanes as a solution in organic solvents. EP-B 771826 describesaqueous binders for coatings and adhesives based on emulsion polymers ofvinyl esters, acrylic or methacrylic esters or vinylaromatics whichcomprise polysiloxanes having unsaturated radicals, for example vinyl,acryloxy or methacryloxy groups, as cross-linkers. EP-A 943634 describesaqueous latices prepared by copolymerization of ethylenicallyunsaturated monomers in the presence of a silicone resin containingsilanol groups for use as coating compositions. EP-A 1095953 describessilicone-grafted vinyl copolymers in which a carbosiloxane dendrimer isgrafted onto the vinyl polymer.

It is known from DE-A 19951877 and WO-A 99/04750 thatsilicone-containing polymers are obtainable by polymerization ofethylenically unsaturated monomers in the presence of a linearpolydialkylsiloxane having polyalkylene oxide side chains. Disadvantagesare the tendency to form coagulum and the broad particle sizedistribution of the products. U.S. Pat. No. 5,216,070 describes aprocess for the inverse emulsion polymerization of carboxyl-functionalmonomers, in which linear polydialkylsiloxanes having polyalkylene oxideside chains are used as emulsifier. DE-A 4240108 describes apolymerization process for preparing polysiloxane-containing binders foruse in dirt-repellent coatings, in which the monomers are polymerized inthe presence of an OH—, COOH— or epoxy-functional polydialkylsiloxanewhich may additionally contain polyether groups. DE-A 10041163 disclosesa process for producing hair cosmetic formulations, in which vinylesters are polymerized in the presence of a polyether-containingcompound, for example polyether-containing silicone compounds.

A disadvantage of the silicone-modified emulsion polymers described inthe prior art is a strong tendency to hydrolyze and to undergouncontrolled crosslinking, which may well be desirable in someapplications and be reinforced subsequently by addition of silane andcatalyst, but in the case of paint dispersions or in coatingcompositions leads to undesirable gel particles (“specks”) and insolubleconstituents. Furthermore, the silicone-containing emulsion polymersknown hitherto are often not resistant to alkali, since silicones areknown to be unstable in an alkaline medium. For this reason, thehydrophobicity and the associated positive properties decrease verygreatly in the systems described hitherto after a relatively long periodof time. Finally, the introduction of a large amount of silanes orsilicones into the emulsion polymers leads to an unsatisfactory particlesize distribution, i.e. the particles become too large and the polymerbecomes inhomogeneous, which can result in serum formation or phaseseparation.

It was an object of the invention to develop polymers which arehydrolysis-resistant and hydrophobic and therefore weathering-stable,water-repellent and nonsoiling and additionally have a good water vaporpermeability and a high wet abrasion resistance. A further object is toprovide a process by means of which hydrophobically modified polymershaving a narrow particle size distribution and no coagulation can beobtained.

The invention provides silicone-containing polymers obtainable by meansof free-radical polymerization of ethylenically unsaturated monomers inthe presence of a polysiloxane, characterized in that

a) from 60 to 99.99% by weight of one or more monomers selected from thegroup consisting of vinyl esters of unbranched or branchedalkylcarboxylic acids having from 1 to 15 carbon atoms, methacrylicesters and acrylic esters of alcohols having 1 to 15 carbon atoms,vinylaromatics, olefins, dienes and vinyl halides are polymerized in thepresence of

b) from 0.01 to 40% by weight of at least one branched polysiloxanewhose lipophilic siloxane part comprises branched structures and whosehydrophilic organopolymer part can be linear or branched, where the % byweight are based on the total weight of a) and b).

Suitable vinyl esters are vinyl esters of unbranched or branchedcarboxylic acids having from 1 to 15 carbon atoms. Preferred vinylesters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalateand vinyl esters of α-branched monocarboxylic acids having from 5 to 13carbon atoms, for example VeoVa9^(R) or VeoVa10^(R) (trade names ofShell). Particular preference is given to vinyl acetate and the greatestpreference is given to a combination of vinyl acetate with α-branchedmonocarboxylic acids having from 5 to 11 carbon atoms, e.g. VeoVa10.

Suitable monomers from the group consisting of esters of acrylic acid ormethacrylic acid are esters of unbranched or branched alcohols havingfrom 1 to 15 carbon atoms. Preferred methacrylic esters or acrylicesters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, propyl acrylate, propyl methacrylate, n-butyl, isobutyland t-butyl acrylate, n-butyl, isobutyl and t-butyl methacrylate,2-ethylhexyl acrylate, norbornyl acrylate. Particular preference isgiven to methyl acrylate, methyl methacrylate, n-butyl, isobutyl andt-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate.

Suitable dienes are 1,3-butadiene and isoprene. Examples ofcopolymerizable olefins are ethene and propene. As vinylaromatics, it ispossible to copolymerize styrene and vinyltoluene. From the groupconsisting of vinyl halides, it is usual to use vinyl chloride,vinylidene chloride or vinyl fluoride, preferably vinyl chloride.

If desired, from 0.05 to 30% by weight, based on the total weight of themonomers a), of one or more auxiliary monomers can additionally becopolymerized. Examples of auxiliary monomers are ethylenicallyunsaturated monocarboxylic and dicarboxylic acids or salts thereof,preferably crotonic acid, acrylic acid, methacrylic acid, fumaric acidand maleic acid; ethylenically unsaturated carboxamides and carboxylicnitriles, preferably acrylamide and acrylonitrile; monoesters anddiesters of fumaric acid and maleic acid, e.g. the diethyl anddiisopropyl esters, and also maleic anhydride, ethylenically unsaturatedsulfonic acids or salts thereof, preferably vinylsulfonic acid,2-acrylamido-2-methylpropanesulfonic acid. Further suitable auxiliarymonomers are cationic monomers such as diallyldimethylammonium chloride(DADMAC), 3-trimethylammoniopropyl(meth)acrylamide chloride (MAPTAC) and2-trimethylammonioethyl (meth)acrylate chloride. Also suitable are vinylethers, vinyl ketones, further vinylaromatic compounds which may alsohave heteroatoms. Suitable auxiliary monomers also include polymerizablesilanes and mercaptosilanes. Preference is given to γ-acryl- orγ-methacryloxypropyltri(alkoxy)silanes,α-methacryloxymethyltri(alkoxy)silanes,γ-methacryloxy-propylmethyldi(alkoxy)silanes,vinylalkyldi(alkoxy)silanes and vinyltri(alkoxy)silanes, with alkoxygroups used being, for example, methoxy, ethoxy, methoxyethylene,ethoxyethylene, methoxypropylene glycol ether or ethoxypropylene glycolether radicals. Examples of such silanes are vinyltrimethoxysilane,vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane,vinyltris(1-methoxy)isopropoxysilane, vinyltributoxysilane,vinyltriacetoxysilane, 3-methacryloxy-propyltrimethoxysilane,3-methacryloxypropylmethyldimethoxysilane,methacryloxymethyltrimethoxysilane,3-methacryloxypropyltris(2-methoxyethoxy)silane, vinyltrichlorosilane,vinylmethyldichlorosilane, vinyltris-(2-methoxyethoxy)silane,trisacetoxyvinylsilane, 3-(triethoxysilyl)propyl(succinicanhydride)silane. Preference is also given to3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and3-mercaptopropylmethyldimethoxysilane.

Further examples are functionalized (meth)acrylates, in particularepoxy-functionalized (meth)acrylates such as glycidyl acrylate, glycidylmethacrylate, allyl glycidyl ether, vinyl glycidyl ether, orhydroxyalkyl-functional (meth)acrylates such as hydroxyethyl(meth)acrylate, or substituted or unsubstituted aminoalkyl(meth)acrylates, or cyclic monomers such as N-vinylpyrrolidone.

Also suitable are polymerizable silicone macromers which have at leastone unsaturated group, e.g. linear or branched polydialkylsiloxaneswhich have a C₁-C₆-alkyl radical and a chain length of from 10 to 1000,preferably from 50 to 500, SiO(C_(n)H_(2n+1))₂ units. These can have oneor two terminal or one or more internal polymerizable groups (functionalgroups). Examples are polydialkylsiloxanes having one or two vinyl,acryloxyalkyl, methacryloxyalkyl or mercaptoalkyl groups, with the alkylgroups being able to be identical or different and having from 1 to 6carbon atoms. Preference is given to α,ω-divinylpolydimethylsiloxanes,α,ω-di(3-acryloxypropyl)polydimethylsiloxanes,α,ω-di(3-methacryloxypropyl)polydimethylsiloxanes,α-monovinylpolydimethylsiloxanes,α-mono(3-acryloxypropyl)polydimethylsiloxanes,α-mono(3-methacryloxypropyl)polydimethylsiloxanes, and also siliconeshaving chain-transferring groups, e.g.α-mono(3-mercaptopropyl)polydimethylsiloxanes orα,ω-di(3-mercaptopropyl)polydimethylsiloxanes. The polymerizablesilicone macromers described in EP-A 614924 are also suitable.

Further examples are precrosslinking comonomers such as multiplyethylenically unsaturated comonomers, for example divinyl adipate,divinylbenzene, diallyl maleate, allyl methacrylate, butanedioldiacrylate or triallyl cyanurate, or postcrosslinking comonomers, forexample acrylamidoglycolic acid (AGA), methyl methylacrylamidoglycolate(MAGME), N-methylolacrylamide (NMA), N-methylolmethacrylamide, allylN-methylolcarbamate, alkyl ethers such as the isobutoxy ethers or estersof N-methylolacrylamide, of N-methylolmethacrylamide and of allylN-methylolcarbamate.

The components a) are preferably selected so that aqueous copolymerdispersions and aqueous redispersions of the copolymer powders whichhave a minimum film formation temperature MFT of <10° C., preferably <5°C., in particular from 0° C. to 2° C., without addition of filmformation aids are obtained. A person skilled in the art will know, onthe basis of the glass transition temperature T_(g), which monomers ormonomer mixtures can be used for this purpose. The glass transitiontemperature T_(g) of the polymers can be determined in a known way bymeans of differential scanning calorimetry (DSC). The T_(g) can also be.calculated approximately beforehand by means of the Fox equation.According to Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956):1/T_(g)=×1/T_(g)1+×2/T_(g)2+ . . . +xn/T_(g)n, where xn is the massfraction (% by weight/100) of the monomer n and T_(g)n is the glasstransition temperature in Kelvin of the homopolymer of the monomer n.T_(g) values for homopolymers are given in the Polymer Handbook 2ndEdition, J. Wiley & Sons, New York (1975).

Preference is given to the copolymer compositions mentioned below:

polymers of vinyl acetate;

vinyl ester copolymers of vinyl acetate with further vinyl esters suchas vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl estersof an alpha-branched carboxylic acid, in particular vinyl esters ofVersatic acid (VeoVa9^(R), VeoVa10^(R));

vinyl ester-ethylene copolymers such as vinyl acetateethylene copolymerswhich may further comprise additional vinyl esters such as vinyllaurate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl esters of analpha-branched carboxylic acid, in particular vinyl esters of Versaticacid (VeoVa9^(R), VeoVa10^(R)), or diesters of fumaric acid or maleicacid;

vinyl ester-ethylene copolymers such as vinyl acetateethylene copolymerswhich may further comprise additional vinyl esters such as vinyllaurate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl esters of analpha-branched carboxylic acid, in particular vinyl esters of Versaticacid (VeoVa9^(R), VeoVa10^(R)) and a polymerizable silicone macromer;

vinyl ester-ethylene-vinyl chloride copolymers in which vinyl acetateand/or vinyl propionate and/or one or more copolymerizable vinyl esterssuch as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoate, vinylesters of an alpha-branched carboxylic acid, in particular vinyl estersof Versatic acid (VeoVa9^(R), VeoVa10^(R)), are preferably present asvinyl esters;

vinyl ester-acrylic ester copolymers with vinyl acetate and/or vinyllaurate and/or vinyl esters of Versatic acid and acrylic esters, inparticular butyl acrylate or 2-ethylhexyl acrylate, which may furthercomprise ethylene;

acrylic ester copolymers, preferably those comprising n-butyl acrylateand/or 2-ethylhexyl acrylate;

methyl methacrylate copolymers, preferably those comprising butylacrylate and/or 2-ethylhexyl acrylate, and/or 1,3-butadiene;

styrene-1,3-butadiene copolymers and styrene(meth)acrylic estercopolymers such as styrene-butyl acrylate, styrene-methylmethacrylate-butyl acrylate or styrene-2-ethylhexyl acrylate, withn-butyl, isobutyl, tert-butyl acrylate being able to be used as butylacrylate.

The greatest preference is given to vinyl esterethylene copolymers suchas vinyl acetate-ethylene copolymers and also copolymers of vinylacetate and ethylene and vinyl esters of an α-branched carboxylic acidhaving 9 or 10 carbon atoms (VeoVa9^(R), VeoVa10^(R)), and in particularcopolymers of vinyl acetate, ethylene, vinyl esters of an α-branchedcarboxylic acid having 9 to 10 carbon atoms (VeoVa9^(R), VeoVa10^(R))with copolymerizable silicone macromers; having an ethylene content ofpreferably from 2 to 30% by weight, which may, if desired, furthercomprise additional auxiliary monomers in the amounts indicated.

The branched polysiloxanes b) comprise structural elements of theformula Y[—C_(n)H_(2n)—(R₂SiO)_(m)-Ap-R₂Si-G]_(x) (I), where

Y is a trivalent to decavalent, preferably trivalent to tetravalent,hydrocarbon radical which may contain one or more heteroatoms selectedfrom the group consisting of oxygen, nitrogen and silicon atoms, theradicals R can be identical or different and are each a monovalent,halogenated or unhalogenated hydrocarbon radical having from 1 to 18carbon atoms per radical,

A is a radical of the formula —R₂Si—R¹—(R₂SiO)_(m)—, where R¹ is adivalent hydrocarbon radical which has from 2 to 30 carbon atoms and canbe interrupted by one or more nonadjacent oxygen atoms, preferably from1 to 4 nonadjacent oxygen atoms,

G is a monovalent radical of the formula —C_(n)H_(2n)-Z or—C_(n)H_(2n−2k)-Z, or a divalent radical —C_(n)H_(2n)—, where the secondbond is to a further radical Y,

Z is a monovalent hydrophilic radical,

x is an integer from 3 to 10, preferably 3 or 4,

k is 0 or 1,

n is an integer from 1 to 12, preferably 2,

m is an integer of at least 1, preferably an integer from 1 to 1000, and

p is 0 or a positive integer, preferably 0 or an integer from 1 to 20,

with the proviso that the branched polysiloxanes have on average atleast one group Z and the group Z contains at least one oxygen atom ornitrogen atom. The polysiloxanes having a branched structure compriseessentially chain-like siloxane blocks whose ends are each connected viaa C_(n)H_(2n) bridge to the structural elements Y and Z. The moresiloxane blocks have elements Y bound to each end, the more branched arethe products produced. In general, the polysiloxanes have a structure inwhich siloxane blocks and organic blocks alternate, with the branchingstructures and the ends consisting of organic blocks. Only stableSi—O—Si bonds or Si—C bonds are present in the molecule. The ratio ofend groups Z to branching groups Y (Z/Y ratio) is preferably from 1.0 to2.0, more preferably from 1.1 to 1.5. The polysiloxanes b) preferablyhave a viscosity of from 50 to 50,000,000 mPa·s at 25° C., morepreferably from 500 to 5,000,000 mPa·s at 25° C. and particularlypreferably from 100 to 1,000,000 mPa·s at 25° C.

Examples of radicals R are alkyl radicals such as the methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,neopentyl, tert-pentyl radicals, hexyl radicals such as the n-hexylradical, heptyl radicals such as the n-heptyl radical, octyl radicalssuch as the n-octyl radical and isooctyl radicals such as the2,2,4-trimethylpentyl radical, nonyl radicals such as the n-nonylradical, decyl radicals such as the n-decyl radical, dodecyl radicalssuch as the n-dodecyl radical and octadecyl radicals such as then-octadecyl radical; cycloalkyl radicals such as the cyclopentyl,cyclohexyl, cycloheptyl and methylcyclohexyl radicals; aryl radicalssuch as the phenyl, naphthyl, anthryl and phenanthryl radicals; alkarylradicals such as the o-, m-, p-tolyl radicals, xylyl radicals andethylphenyl radicals; and aralkyl radicals such as the benzyl radical,the α- and the β-phenylethyl radical.

Examples of halogenated radicals R are haloalkyl radicals such as the3,3,3-trifluoro-n-propyl radical, the 2,2,2,2′,2′,2′-hexafluoroisopropylradical, the heptafluoroisopropyl radical and haloaryl radicals such asthe o-, m- and p-chlorophenyl radicals.

The radical R is preferably a monovalent hydrocarbon radical having from1 to 6 carbon atoms, with the methyl radical being particularlypreferred.

Examples of radicals R¹ are radicals of the formulae —(CH₂)₂—, —(CH₂)₄—,—(CH₂)₆—, —(CH₂)₈—, —(CH₂)₁₀—, —C₆H₄—, —C₂H₄C₆H₄C₂H₄—,—CH₂CH(CH₃)CH₆H₄CH(CH₃)CH₂— and —C₂H₄-norbornanediyl-.

Examples of the radical Y are radicals of the formulae

with the radical of the formula

being particularly preferred.

Preferred radicals Z are derived from hydrophilic building blocks whichcan be present in monomeric, oligomeric or polymeric form and whosesolubility in water under standard conditions (DIN 50014, 23/50) is ≧1g/l. The molecular weight of the radicals Z is generally from 30 to 10000.

Examples of polymeric radicals are polyols, polyethers such aspolyalkylene oxides, preferably having methylene oxide, ethylene oxide(EO) or propylene oxide (PO) units or mixtures of these alkylene oxideunits. Further examples are polyacids and salts thereof, preferablypoly(meth)acrylic acid. Further suitable polymeric radicals arepolyester, polyurea or polycarbonate radicals. Copolymers of(meth)acrylic ester monomers which further comprise comonomer unitshaving functional groups such as carboxyl, amide, sulfonate,dialkylammonium and trialkylammonium groups are also suitable. Preferred(meth)acrylic ester monomers are those which have been mentioned above.As functional comonomers, preference is given to those mentioned underthe auxiliary monomers a). The greatest preference is given tohomocondensates and cocondensates of ethylene oxide and propylene oxide.

Examples of monomeric and oligomeric radicals Z are those havinghydroxyl groups, carboxyl groups and salts thereof, sulfonic acid groupsand salts thereof, sulfate groups, ammonium groups, keto groups, ethergroups, ester groups, amide groups. Preference is given to radicals Zhaving an anionic or cationic charge, and also those having azwitterionic structure. Further examples are:

—(CH₂)₁₋₆—O—CH₂—CHOH—CH₂—SO₃—Na⁺,

—(CH₂)₁₋₆—O—CH₂—CHOH—CH₂—N⁺(CH₃)₂CH₂CO₂ ⁻,

—(CH₂)₁₋₆-(EO)₁₀₋₂₀—O—CH₃,

—(CH₂)₁₋₆—O—SO₃—H₃N⁺—CH(CH₃)₂,

—(CH₂)₁₋₆—N⁺(CH₃)₂—(CH₂)₁₋₆—SO₃ ⁻,

—(CH₂)₁₋₆—O-(EO)₁₀₋₂₀—H,

—(CH₂)₁₋₆—CHOH—CH₂—N⁺(CH₃)₂CH₂CO₂ ⁻,

—(CH₂)₁₋₆—CHOH—CH₂—N⁺(CH₃)₂—CH(CH₃)CH₂—CO₂ ⁻.

Methods of preparing the branched polysiloxanes b) are known to thoseskilled in the art and are, for example, known from DE-A 10135305.

The silicone-containing polymers are prepared by means of free-radicalpolymerization in an aqueous medium, preferably emulsion polymerization.The polymerization is usually carried out in a temperature range from20° C. to 100° C., in particular from 45° C. to 80° C. Thepolymerization is initiated by means of the customary free-radicalinitiators which are preferably used in amounts of from 0.01 to 3.0% byweight, based on the total weight of the monomers. As initiators,preference is given to using inorganic peroxides such as ammonium,sodium, potassium peroxodisulfate or hydrogen peroxide, either alone orin combination with reducing agents such as sodium sulfite, sodiumhydrogensulfite, sodium formaldehydesulfoxylate or ascorbic acid. It isalso possible to use water-soluble organic peroxides, for examplet-butyl hydroperoxide, cumene hydroperoxide, usually in combination withreducing agents, or else water-soluble azo compounds. In the case of acopolymerization using gaseous monomers such as ethylene and vinylchloride, the polymerization is carried out under superatmosphericpressure, generally in the range from 1 to 100 bar_(abs).

To stabilize the dispersion, it is possible to use not only thepolysiloxane component b) but also, in addition, anionic and nonionicemulsifiers and also protective colloids. Preference is given to usingnonionic or anionic emulsifiers, preferably a mixture of nonionic andanionic emulsifiers. As nonionic emulsifiers, preference is given tocondensation products of ethylene oxide or propylene oxide with linearor branched alcohols having from 8 to 18 carbon atoms, alkylphenols orlinear or branched carboxylic acids having from 8 to 18 carbon atoms,and also block copolymers of ethylene oxide and propylene oxide.Suitable anionic emulsifiers are, for example, alkylsulfates,alkysulfonates, alkylarylsulfates and also sulfates or phosphates ofcondensation products of ethylene oxide with linear or branched alkylalcohols having from 5 to 25 EO units, alkylphenols and monoesters ordiesters of sulfosuccinic acid. The amount of emulsifier is from 0.01 to40% by weight, based on the total weight of the monomers a) used.

If appropriate, protective colloids can also be used. Examples ofsuitable protective colloids are polyvinyl alcohols having a content offrom 75 to 95 mol %, preferably from 84 to 92 mol %, of vinyl alcoholunits; poly-N-vinylamides such as polyvinylpyrrolidones; polysaccharidessuch as starches, and also celluloses and their carboxymethyl, methyl,hydroxyethyl, hydroxypropyl derivatives; synthetic polymers such aspoly(meth)acrylic acid, poly(meth)acrylamide. Particular preference isgiven to using the polyvinyl alcohols mentioned. The protective colloidsare generally used in an amount of from 0.05 to 10% by weight, based onthe total weight of the monomers a) used.

If appropriate, the molecular weight can be controlled by means of thecustomary regulators, for example alcohols such as isopropanol,aldehydes such as acetaldehyde, chlorine-containing compounds,mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan,mercaptopropionic acid (esters). To set the pH, pH-regulating compoundssuch as sodium acetate or formic acid can be used in the preparation ofthe dispersion.

The polymerization can be carried out independently of thepolymerization process with or without use of seed latices, with all orsome constituents of the reaction mixture being initially charged, orwith part being initially charged and the or some of the constituents ofthe reaction mixture subsequently being metered in, or by the feedstream process without an initial charge. The comonomers a) and, ifappropriate, the auxiliary monomers can all be initially charged for thepreparation of the dispersion (batch process), or part of the monomersis initially charged and the remainder is metered in (semibatchprocess).

To prepare the dispersion, the component b) can be initially charged ormetered in, or part is initially charged and the remainder is meteredin. The surface-active substances can be metered in alone or as apreemulsion with the comonomers.

In the copolymerization of gaseous monomers a) such as ethylene, thedesired amount is introduced by setting of a particular pressure. Thepressure under which the gaseous monomer is introduced can be setinitially to a particular value and can decrease during thepolymerization, or the pressure is kept constant during the entirepolymerization. The latter embodiment is preferred.

After the polymerization is complete, an after-polymerization usingknown methods can be carried out to remove residual monomers, forexample an after-polymerization initiated by means of redox catalysts.Volatile residual monomers and further volatile, nonaqueous constituentsof the dispersion can also be removed by means of distillation,preferably under reduced pressure, and, if appropriate, with inertentrainer gases such as air, nitrogen or steam being passed through orover the reaction mixture.

The aqueous dispersions which can be obtained by the process of theinvention have a solids content of from 30 to 70% by weight, preferablyfrom 45 to 65% by weight. To prepare polymer powders, in particularwater-redispersible polymer powders, the aqueous dispersions are dried,if appropriate after addition of protective colloids as atomizationaids, for example by means of fluidized-bed drying, freeze drying orspray drying. The dispersions are preferably spray dried. Spray dryingis carried out in customary spray-drying units, with atomization beingable to be effected by means of single-fluid, two-fluid or multifluidnozzles or by means of a rotary disk. The added temperature is generallyin the range from 45° C. to 120° C., preferably from 60° C. to 90° C.,depending on the unit, the T_(g) of the resin and the desired degree ofdrying.

In general, the atomization aid is used in a total amount of from 3 to30% by weight, based on the polymeric constituents of the dispersion.Suitable atomization aids are the abovementioned protective colloids.When carrying out the atomization, a content of up to 1.5% by weight ofantifoam, based on the base polymer, has frequently been found to beadvantageous. To improve the blocking stability, the powder obtained canbe mixed with an antiblocking agent (anticaking agent), preferably in anamount of up to 30% by weight, based on the total weight of polymericconstituents. Examples of antiblocking agents are Ca carbonate or Mgcarbonate, talc, gypsum, silica, kaolins, silicates.

Emulsion polymers which are hydrophobic, weathering-stable,water-repellent, very resistant and nonsoiling and additionally have agood water vapor permeability are obtained.

The silicone-containing polymers in the form of their aqueousdispersions and in the form of their polymer powders, in particularwater-redispersible polymer powders, are suitable for use in adhesivesand coating compositions, for the consolidation of fibers or otherparticulate materials, for example for the textile sector. They are alsosuitable as modifiers and as hydrophobicizing agents. They can also beused advantageously in polishes and in cosmetics, e.g. in the field ofhair care. Furthermore, they are suitable as binders in adhesives andcoating compositions, including as protective coating, e.g. for metals,films, wood, or as release coating, e.g. for paper treatment. They areparticularly useful as binders for paints, adhesives and coatingcompositions in the building sector, for example in tile adhesives andthermal insulation adhesives, and in particular for use in low-emissionplastic emulsion paints and plastic emulsion renders, both for interioruse and for exterior use. The formulations for emulsion paints andemulsion renders are known to those skilled in the art and generallycomprise from 5 to 50% by weight of the silicone-containing polymers,from 5 to 35% by weight of water, from 5 to 80% by weight of filler,from 5 to 30% by weight of pigments and from 0.1 to 10% by weight offurther additives, with the percentages by weight in the formulationadding up to 100% by weight.

Examples of fillers which can be used are carbonates such as calciumcarbonate in the form of dolomite, calcite and chalk. Further examplesare silicates such as magnesium silicate in the form of talc or aluminumsilicates such as clay and clay minerals; quartz flour, silica sand,finely divided silica, feldspar, barite and gypsum. Fibrous fillers arealso suitable. In practice, use is frequently made of mixtures ofdifferent fillers. For example, mixtures of fillers having a differentparticle size or mixtures of carbonaceous and siliceous fillers. In thelatter case, formulations having a proportion of more than 50% byweight, in particular more than 75% by weight, of carbonate or silicatein the total filler are referred to as carbonate-rich or silicate-richformulations.

Plastic renders generally comprise coarser-grained fillers than emulsionpaints. The particle size is in this case often in the range from 0.2 to5.0 mm. Otherwise, plastic renders can comprise the same additives asemulsion paints.

Suitable pigments are, for example, titanium dioxide, zinc oxide, ironoxides, carbon black as inorganic pigments, and also the customaryorganic pigments. Examples of further additives are wetting agents inproportions of generally from 0.1 to 0.5% by weight, based on the totalweight of the formulation. Examples are sodium and potassiumpolyphosphates, polyacrylic acids and salts thereof. Further additiveswhich may be mentioned are thickeners which are generally used in anamount of from 0.01 to 2.0% by weight, based on the total weight of theformulation. Thickeners which can be used are cellulose ethers, starchesor bentonite as an example of an inorganic thickener. Further additivesare preservatives, antifoams, antifreezers.

To produce the adhesives and coating compositions, the polymerdispersion or the polymer powder is mixed with the further constituentsof the formulation, viz. filler and further additives, in suitablemixers and homogenized. If desired, the polymer powder can also be addedin the form of an aqueous redispersion on the building site. In manycases, a dry mix is prepared and the water necessary for processing isadded immediately before processing. In the production of paste-likecompositions, a frequently employed procedure is to initially charge thewater, add the dispersion and finally stir in the solids.

The silicone-containing polymers are particularly advantageous asbinders in coating formulations for low-emission interior paints, inparticular those having a high PVK (highly filled paints), or ashydrophobicizing binder for renders.

The following examples serve to illustrate the invention withoutrestricting it in any way.

Raw materials:

Genapol ×150:

Ethoxylated isotridecyl alcohol having a degree of ethoxylation of 15.

Genapol PF80:

EO-PO block polymer containing 80% of EO.

Mersolat:

Na alkylsulfonate having from 12 to 14 carbon atoms in the alkylradical.

Polyvinyl alcohol W25/140:

Polyvinyl alcohol having a viscosity of about 25 mPas (20° C., 4%strength solution, measured by the Höppler method) and a saponificationnumber of 140 (mg of KOH/g of polymer) (degree of hydrolysis: 88 mol %).

PDMS mixture:

Product of Wacker-Chemie GmbH: DEHESIVE 929, a linearpolydimethylsiloxane having 78 mol % of vinyl end groups.

Preparative Examples for the Branched Polysiloxane—Component b)

In a glass flask provided with a mechanical stirrer, 108 g of1,2,4-trivinylcyclohexane are mixed with 1840 g of anα,ω-dihydrogenpolymethylsiloxane having a content of active hydrogen(Si-bonded hydrogen) of 0.18% by weight and a viscosity of 9 mPas at 25°C. and 1.9 g of a solution of aplatinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex indimethylpolysiloxane (known as Karstedt catalyst) having a Pt content of1.0% by weight are subsequently added. The reaction mixture heats up toabout 80° C. in a few minutes and is stirred at this temperature forabout 1 hour. A branched siloxane polymer having a viscosity of 220mm²/s at 25° C. and a content of active hydrogen of 0.067% by weight isobtained. In accordance with the principle of the synthesis, all freesiloxane chain ends consist of the highly reactive hydrogendimethylsiloxy units.

The total amount of the highly branched SiH-functional siloxane polymeris mixed with 3200 g of a monoallyl-terminated polyether composed ofequal molar amounts of ethyleneoxy and propyleneoxy groups and having anaverage molecular weight (M_(n)) of 1880 Da, activated by means of 5 gof a solution of hexachloroplatinic acid in isopropanol (0.5% Ptcontent) and heated to 100° C. After the mixture becomes clear, it isallowed to react further for 1 hour, after which a conversion of >98% isachieved. The highly branched polyether-siloxane copolymer has aviscosity of 6800 m²/s and a polyether content of about 62% by weight.It can be dispersed homogeneously in water without use of furtherauxiliaries.

COMPARATIVE EXAMPLE 1 Vinyl acetate-ethylene-vinylsilane copolymerwithout component b

102.99 kg of water, 17.90 kg of Genapol ×150 (40% strength aqueoussolution), 3.54 kg of Mersolat (40% strength aqueous solution), 1.97 kgof sodium vinylsulfonate (25% strength), 13.95 kg of W 25/140 (polyvinylalcohol, 10% strength in water) and 24.69 kg of vinyl acetate wereplaced in a 572 liter pressure autoclave. The mixture was brought to apH of 5 by means of 10% strength formic acid. In addition, 314 ml ofTrilon B (EDTA; 2% strength aqueous solution) and 991 ml of ammoniumiron sulfate (1% strength solution) were added. The autoclave was heatedto 70° C. and pressurized with 22 bar of ethylene. As soon as thereactor was in thermal equilibrium, a 10.0% strength ammoniumperoxodisulfate solution (APS solution) was introduced at 1023 g perhour and a 5.05% strength sodium sulfite solution was introduced at 1976g per hour. 25 minutes later, metered addition of a mixture of 217.25 kgof vinyl acetate and 1.25 kg of vinyltrimethoxysilane (Wacker Silan XL10) at a rate of 41.23 kg per hour (metered addition of monomer) wascommenced.

At the same time, an emulsifier mixture was introduced at a meteringrate of 9.85 kg per hour. The emulsifier mixture comprised 22.34 kg ofwater, 12.96 kg of Genapol ×150 (40% strength aqueous solution) and13.95 kg of W 25/140 (polyvinyl alcohol; 10% strength solution).

The total addition time for the metered addition of monomer was 5.3hours and the total addition time for the metered addition of theemulsifier mixture was 5.0 hours.

15 minutes after the commencement of the reaction, the metered additionof APS was reduced to 636 g per hour, and the metered addition of Nasulfite was reduced to 1226 g per hour.

30 minutes after the end of the metered addition of emulsifier, the “GMAmixture” was introduced. Composition of the “GMA mixture”: 4.94 kg ofvinyl acetate and 1.48 kg of glycidyl methacrylate. The metering timewas

30 minutes (rate: 12.84 kg per hour). After the “GMA mixture” had allbeen added, the metered addition of APS and Na sulfite was continued for1 hour. After depressurization, the dispersion was treated with steam(“stripped”) to minimize residual monomers and Hydorol W wassubsequently added as preservative.

Dispersion analyses: see Table 1

COMPARATIVE EXAMPLE 2 Vinyl acetate-VeoVa-ethylene-vinylsilane-GMA-PDMScopolymer without component b

76.80 kg of water, 27.12 kg of W 25/140 (polyvinyl alcohol; 10% strengthsolution), 4.80 kg of Genapol ×150 (40% strength aqueous solution), 3.44kg of Mersolat (40% strength aqueous solution), 1.92 kg of sodiumvinylsulfonate (25% strength), 18.00 kg of vinyl acetate, 4.80 kg ofPDMS mixture and 18.00 kg of VeoVa 10 were placed in a 572 literpressure autoclave. The mixture was brought to a pH of 5 by means of 10%strength formic acid. In addition, 314 ml of Trilon B (EDTA; 2% strengthaqueous solution) and 991 ml of ammonium iron sulfate (1% strengthsolution) were added. The autoclave was heated to 70° C. and pressurizedwith 13 bar of ethylene. As soon as the reactor was in thermalequilibrium, a 10.0% strength ammonium peroxodisulfate solution (APSsolution) was introduced at 1023 g per hour and a 5.05% strength sodiumsulfite solution was introduced at 1976 g per hour. 25 minutes later,metered addition of a mixture of 166.80 kg of vinyl acetate, 29.28 kg ofVeoVa 10 and 1.22 kg of vinyltrimethoxysilane (Wacker Silan XL 10) at arate of 34.02 kg per hour (metered addition of monomer) was commenced.

At the same time, an emulsifier mixture was introduced at a meteringrate of 12.89 kg per hour. The emulsifier mixture comprised 45.69 kg ofwater and 25.20 kg of Genapol ×150 (40% strength aqueous solution). Thetotal addition time for the metered addition of monomer was 5.8 hoursand the total addition time for the metered addition of the emulsifiermixture was 5.5 hours.

15 minutes after the commencement of the reaction, the metered additionof APS was reduced to 636 g per hour, and the metered addition of Nasulfite was reduced to 1226 g per hour.

30 minutes after the end of the metered addition of emulsifier, the “GMAmixture” was introduced. Composition of the “GMA mixture”: 4.80 kg ofvinyl acetate, 720.01 g of VeoVa 10 and 2.88 kg of glycidylmethacrylate. The metering time was 30 minutes (rate: 16.8 kg per hour).After the “GMA mixture” had all been added, the metered addition of APSand Na sulfite was continued for 1 hour. After depressuration, thedispersion was treated with steam (“stripped”) to minimize residualmonomers and Hydorol W was subsequently added as preservative.

Dispersion analyses: see Table 1

COMPARATIVE EXAMPLE 3 Vinyl acetate-VeoVa-ethylene-vinylsilane-GMA-PDMScopolymer without component b

75.80 kg of water, 28.28 kg of W 25/140 (polyvinyl alcohol; 10% strengthsolution), 10.43 kg of Genapol PF 80 (19.2% strength aqueous solution),3.58 kg of Mersolat (40% strength aqueous solution), 2.00 kg of sodiumvinylsulfonate (25% strength), 230.24 g of sodium acetate (100% pure),18.77 kg of vinyl acetate, 5.01 kg of PDMS mixture and 18.77 kg of VeoVa10 were placed in a 572 liter pressure autoclave. The mixture wasbrought to a pH of 5 by means of 10% strength formic acid. In addition,314 ml of Trilon B (EDTA; 2% strength aqueous solution) and 991 ml ofammonium iron sulfate (1% strength solution) were added. The autoclavewas heated to 70° C. and pressurized with 13 bar of ethylene. As soon asthe reactor was in thermal equilibrium, a 10.0% strength ammoniumperoxodisulfate solution (APS solution) was introduced at 1023 g perhour and a 5.05% strength sodium sulfite solution was introduced at 1976g per hour. 25 minutes later, metered addition of a mixture of 173.93 kgof vinyl acetate, 30.53 kg of VeoVa 10 and 1.28 kg ofvinyltrimethoxysilane (Wacker Silan XL 10) at a rate of 35.48 kg perhour (metered addition of monomer) was commenced.

At the same time, an emulsifier mixture was introduced at a meteringrate of 12.31 kg per hour. The emulsifier mixture comprised 12.18 kg ofwater and 54.74 kg of Genapol PF 80 (19.2% strength aqueous solution).The total addition time for the metered addition of monomer was 5.8hours and the total addition time for the metered addition of theemulsifier mixture was 5.5 hours.

15 minutes after the commencement of the reaction, the metered additionof APS was reduced to 636 g per hour, and the metered addition of Nasulfite was reduced to 1226 g per hour.

30 minutes after the end of the metered addition of emulsifier, the “GMAmixture” was introduced. Composition of the “GMA mixture”: 5.01 kg ofvinyl acetate, 750.78 g of VeoVa 10 and 3.00 kg of glycidylmethacrylate. The metering time was 30 minutes (rate: 17.52 kg perhour). After the “GMA mixture” had all been added, the metered additionof APS and Na sulfite was continued for 1 hour. After depressurization,the dispersion was treated with steam (“stripped”) to minimize residualmonomers and Hydorol W was subsequently added as preservative.

Dispersion analyses: see Table 1

EXAMPLE 4 Copolymer Analogous to Comparative Ex. 2 with Component b

2.60 kg of water, 298.04 g of W 25/140 (polyvinyl alcohol; 10% strengthsolution), 212.88 kg of Genapol ×150 (40% strength aqueous solution),157.9 g of Mersolat (30% strength aqueous solution), 68.12 g of sodiumvinylsulfonate (25% strength), 851.53 g of vinyl acetate, 170.31 g ofPDMS mixture and 851.53 g of VeoVa 10 were placed in a 19 liter pressureautoclave. The mixture was brought to a pH of 5 by means of 10% strengthformic acid. In addition, 9.7 ml of Trilon B (EDTA; 2% strength aqueoussolution) and 30.6 ml of ammonium iron sulfate (1% strength solution)were added. The autoclave was heated to 70° C. and pressurized with 14bar of ethylene. As soon as the reactor was in thermal equilibrium, a5.41% strength ammonium peroxodisulfate solution (APS solution) wasintroduced at 68 g per hour and a 4.16% strength sodium sulfite solutionwas introduced at 85 g per hour. 25 minutes later, metered addition of amixture of 5.79 kg of vinyl acetate, 825.98 g of VeoVa 10 and 43.54 g ofvinyltrimethoxysilane (Wacker Silan XL 10) at a rate of 1149 g per hour(metered addition of monomer) was commenced.

At the same time, an emulsifier mixture was introduced at a meteringrate of 433 g per hour. The emulsifier mixture comprised 2.04 kg ofwater and 340.61 g of component b). The total addition time for themetered addition of monomer was 5.8 hours and the total addition timefor the metered addition of the emulsifier mixture was 5.5 hours.

15 minutes after the commencement of the reaction, the metered additionof APS was reduced to 42.2 g per hour, and the metered addition of Nasulfite was reduced to 52.7 g per hour.

30 minutes after the end of the metered addition of emulsifier, the “GMAmixture” was introduced. Composition of the “IGMA mixture”: 170.31 g ofvinyl acetate, 25.55 g of VeoVa 10 and 51.09 g of glycidyl methacrylate.The metering time was 30 minutes (rate: 494 g per hour). After the “GMAmixture” had all been added, the metered addition of APS and Na sulfitewas continued for 1 hour. After depressurization, the dispersion wastreated with steam (“stripped”) to minimize residual monomers andHydorol W was subsequently added as preservative.

Dispersion analyses: see Table 1

EXAMPLE 5 Analogous to Example 4 without Mersolat

2.16 kg of water, 955.94 g of W 25/140 (polyvinyl alcohol; 10% strengthsolution), 84.60 g of component b), 156.87 g of Mersolat (30% strengthaqueous solution), 67.68 g of sodium vinylsulfonate (25% strength),845.96 g of vinyl acetate, 169.19 g of PDMS mixture and 845.96 g ofVeoVa 10 were placed in a 19 liter pressure autoclave. The mixture wasbrought to a pH of 5 by means of 10% strength formic acid. In addition,9.7 ml of Trilon B (EDTA; 2% strength aqueous solution) and 30.6 ml ofammonium iron sulfate (1% strength solution) were added. The autoclavewas heated to 70° C. and pressurized with 14 bar of ethylene. As soon asthe reactor was in thermal equilibrium, a 5.41% strength ammoniumperoxodisulfate solution (APS solution) was introduced at 68 g per hourand a 4.16% strength sodium sulfite solution was introduced at 85 g perhour. 25 minutes later, metered addition of a mixture of 5.75 kg ofvinyl acetate, 820.58 g of VeoVa 10 and 43.16 g of vinyltrimethoxysilane(Wacker Silan XL 10) at a rate of 1142 g per hour (metered addition ofmonomer) was commenced.

At the same time, an emulsifier mixture was introduced at a meteringrate of 431 g per hour. The emulsifier mixture comprised 2.03 kg ofwater and 338.38 g of component b). The total addition time for themetered addition of monomer was 5.8 hours and the total addition timefor the metered addition of the emulsifier mixture was 5.5 hours.

15 minutes after the commencement of the reaction, the metered additionof APS was reduced to 42.2 g per hour, and the metered addition of Nasulfite was reduced to 52.7 g per hour.

30 minutes after the end of the metered addition of emulsifier, the “GMAmixture” was introduced. Composition of the “IGMA mixture”: 169.19 g ofvinyl acetate, 25.38 g of VeoVa 10 and 50.76 g of glycidyl methacrylate.The metering time was 30 minutes (rate: 491 g per hour). After the “GMAmixture” had all been added, the metered addition of APS and Na sulfitewas continued for 1 hour. After depressurization, the dispersion wastreated with steam (“stripped”) to minimize residual monomers andHydorol W was subsequently added as preservative.

Dispersion analyses: see Table 1

EXAMPLE 6

The procedure of Example 5 was repeated, but without addition ofpolyvinyl alcohol.

Dispersion analyses: see Table 1.

EXAMPLE 7 Analogous to Example 5 with Less Polyvinyl Alcohol

2.23 kg of water, 425.65 g of W 25/140 (polyvinyl alcohol; 10% strengthsolution), 567.54 g of component b) (15% strength aqueous solution),157.86 g of Mersolat (30% strength aqueous solution), 68.10 g of sodiumvinylsulfonate (25% strength), 851.31 g of vinyl acetate, 170.26 g ofPDMS mixture and 851.31 g of VeoVa 10 were placed in a 19 liter pressureautoclave. The mixture was brought to a pH of 5 by means of 10% strengthformic acid. In addition, 9.7 ml of Trilon B (EDTA; 2% strength aqueoussolution) and 30.6 ml of ammonium iron sulfate (1% strength solution)were added. The autoclave was heated to 70° C. and pressurized with 14bar of ethylene. As soon as the reactor was in thermal equilibrium, a5.41% strength ammonium peroxodisulfate solution (APS solution) wasintroduced at 68 g per hour and a 4.16% strength sodium sulfite solutionwas introduced at 85 g per hour. 25 minutes later, metered addition of amixture of 5.79 kg of vinyl acetate, 825.77 g of VeoVa 10 and 43.43 g ofvinyltrimethoxysilane (Wacker Silan XL 10) at a rate of 1149 g per hour(metered addition of monomer) was commenced.

At the same time, an emulsifier mixture was introduced at a meteringrate of 413 g per hour. The emulsifier mixture comprised 2.27 kg ofcomponent b) (15% strength aqueous solution). The total addition timefor the metered addition of monomer was 5.8 hours and the total additiontime for the metered addition of the emulsifier mixture was 5.5 hours.

15 minutes after the commencement of the reaction, the metered additionof APS was reduced to 42.2 g per hour, and the metered addition of Nasulfite was reduced to 52.7 g per hour.

30 minutes after the end of the metered addition of emulsifier, the “GMAmixture” was introduced. Composition of the “GMA mixture”: 170.26 g ofvinyl acetate, 25.54 g of VeoVa 10 and 51.08 g of glycidyl methacrylate.The metering time was 30 minutes (rate: 494 g per hour). After the “GMAmixture” had all been added, the metered addition of APS and Na sulfitewas continued for 1 hour. After depressurization, the dispersion wastreated with steam (“stripped”) to minimize residual monomers andHydorol W was subsequently added as preservative.

Dispersion analyses:

see Table 1

EXAMPLE 8 Copolymer without Silicone Macromer

2.04 kg of water, 221.50 g of Genapol ×150 (40% strength aqueoussolution), 164.30 g of Mersolat (30% strength aqueous solution), 70.88 gof sodium vinylsulfonate (25% strength) and 886.0 g of vinyl acetatewere placed in a 19 liter pressure autoclave. The mixture was brought toa pH of 5 by means of 10% strength formic acid. In addition, 9.7 ml ofTrilon B (EDTA; 2% strength aqueous solution) and 30.6 ml of ammoniumiron sulfate (1% strength solution) were added. The autoclave was heatedto 70° C. and pressurized with 22 bar of ethylene. As soon as thereactor was in thermal equilibrium, a 5.41% strength ammoniumperoxodisulfate solution (APS solution) was introduced at 68 g per hourand a 4.16% strength sodium sulfite solution was introduced at 85 g perhour. 25 minutes later, metered addition of a mixture of 6.91 kg ofvinyl acetate and 45.20 g of vinyltrimethoxysilane (Wacker Silan XL 10)at a rate of 1200 g per hour (metered addition of monomer) wascommenced.

At the same time, an emulsifier mixture was introduced at a meteringrate of 611 g per hour. The emulsifier mixture comprised 1000.0 g of W25/140 (polyvinyl alcohol; 10% strength solution) and 2.36 kg ofcomponent b) (15% strength aqueous solution). The total addition timefor the metered addition of monomer was 5.8 hours and the total additiontime for the metered addition of the emulsifier mixture was 5.5 hours.

15 minutes after the commencement of the reaction, the metered additionof APS was reduced to 42.2 g per hour, and the metered addition of Nasulfite was reduced to 52.7 g per hour.

30 minutes after the end of the metered addition of emulsifier, the “GMAmixture” was introduced. Composition of the “GMA mixture”: 177.20 g ofvinyl acetate and 53.16 g of glycidyl methacrylate. The metering timewas 30 minutes (rate: 462 g per hour). After the “GMA mixture” had allbeen added, the metered addition of APS and Na sulfite was continued for1 hour.

After depressurization, the dispersion was treated with steam(“stripped”) to minimize residual monomers and Hydorol W wassubsequently added as preservative.

Dispersion analyses: see Table 1 TABLE 1 Dispersion analyses Tg BF 20 DDn Dv SA SC Ex. ° C. pH mPas nm μm μm M² % C1 10.3 5.15 8400 317 0.080.314 26.7 59.7 C2 9.2 5.18 3220 390 0.08 0.759 16.7 58.0 C3 14.7 5.2011 600 410 0.12 0.650 14.7 58.7 4 11.3 4.97 780 430 0.14 0.802 9.5 59.35 12.2 5.00 5280 503 0.20 0.921 9.2 59.9 6 13.0 5.20 490 245 0.09 0.69215.8 58.9 7 12.9 4.80 510 419 0.10 0.891 8.9 59.2 8 12.3 5.00 3000 3050.08 0.492 20.3 55.9BF 20 = Brookfield viscosity,D = mean particle size (Nanosizer),Dn = mean particle size (number average, Coulter Counter),Dv = mean particle size (volume average, Coulter Counter),SA = mean particle surface area per g of polymer dispersionSC = solids content.

In Comparative Examples 1 to 3, emulsifiers and protective colloidsknown from the prior art were used for the emulsion polymerization. InExamples 4 to 8, branched polysiloxanes (component b) were used asemulsifiers.

As can be seen from Table 1, polymer dispersions having a proportion ofsilicone and an advantageous particle size distribution were obtained,and coagulum formation was not observed in a single case. The viscositycan be varied over a wide range via the amount of protective colloid(here polyvinyl alcohol W25/140) (Examples 5 and 7).

The dispersions were used to produce paints having a silicate-richformulation 1 and a carbonate-rich formulation 2 in accordance with theformulations presented below (Tables 2 and 3): TABLE 2 Paint formulation1 (silicate-rich): Water 350 Cellulose ether (Tylose MH 10 000 KG4) 5Dispersant (Dispex N 40) 2 Magnesium silicate (talc N) 100 Magnesiumsilicate (China clay grade B) 100 Titanium dioxide pigment (Kronos 2300)100 Calcium carbonate (Omyacarb 5 GU) 200 Ammonia 0.5 Polymer dispersion(SC 60%) 142.5 Total parts by weight 1000

TABLE 3 Paint formulation 2 (carbonate-rich): Water 350 Cellulose ether(Tylose MH 10 000 KG4) 5 Dispersant (Dispex N 40) 2 Titanium dioxidepigment (Kronos 2300) 100 Calcium carbonate (Omyacarb 5 GU) 400 Ammonia0.5 Polymer dispersion (SC 60%) 142.5 Total parts by weight 1000

The dispersions were also used to produce renders in accordance with theformulation presented below (Table 4): TABLE 4 Render formulation 3Water 91.2 Dispersant (Dispex N 40) 2 Fungicide (Parmetol A23) 2 Sheetsilicate thickener (Bentone EW, 5% strength) 15 Methylcellulosethickener (Tylose MH 10 000 KG4, 30 2% strength) Acrylate thickener(Rohagit SD 15) 1 Algicide (Algon P) 1 Ammonia 0.5 Cellulose fibers(Arbocel B400) 3 Dralon fibers (Dralon fibers 6.7/4 mm) 2 Titaniumdioxide (Kronos 2190) 20 Kieselguhr (Celite 281) 40 Chalk (Calcilit 100)360 Chalk (Calcilit 1.5-2 mm) 320 Antifoam (Agitan 260) 1 Polymerdispersion (60% strength) 111.3 Total parts by weight 1000Use Tests:

Testing of the hydrophobicity by means of the water drop test

A render produced according to the above formulation 3 was applied bymeans of a spatula to 3 conventional, commercially available lime-sandbricks (dimensions: 10×10×5 cm) to particle size (about 2 mm, total ofabout 30-40 g of render per brick). After drying, 1 ml of water wasplaced in the form of a drop on the render by means of a syringe after 7days. The time (in min) until the drop had spread and thus disappearedwas recorded. The longer this time, the higher the hydrophobicity andthe water resistance of the render or the dispersion present therein. Inthe case of a hydrophilic dispersion, the drop has disappeared after notmore than 10 minutes, while it remains for a number of hours in the caseof hydrophobic dispersions.

An analogous test was carried out using the paint formulations 1 and 2.However, these were applied in a layer thickness of about 400 μm to acommercial fibrocement sheet (Esterplan). Here too, the longer the dropremains, the more hydrophobic is the dispersion.

Table 5 shows the use data. TABLE 5 Hydrophobicity HydrophobicityHydrophobicity Formulation 2 Formulation 1 Formulation 3 after 1 day inafter 1 day in after 7 days Example min min in min C1 120 110  5 C2 notmeasured C3 not measured 4 410 400 160 5 390 370 175 6 410 420 180 7 430460 200 8 360 350 100

The following can be seen from Table 5:

Comparison of Comparative Example 1 with Example 8 shows that thehydrophobicity can be increased significantly in all formulations whenthe silicone-containing polymer is used. As a comparison of Example 8(copolymer without silicone macromer) with Examples 4, 5, 6 and 7 shows,the hydrophobicity can be improved further to an appreciable extent if apolymerizable silicone macromer is additionally copolymerized into thesilicone-containing polymer.

1-22. (canceled)
 23. A silicone-containing addition polymer, prepared bythe process comprising free-radically polymerizing a) from 60 to 99.99%by weight of at least one monomer selected from the group consisting ofvinyl esters of unbranched or branched C₁₋₁₅ alkylcarboxylic acids,methacrylic esters and acrylic esters of C₁₋₁₅ alcohols, vinylaromatics,monoolefins, dienes, and vinyl halides, in the presence of b) from 0.01to 40% by weight of at least one branched polysiloxane having lipophilicand hydrophilic portions, at least one lipophilic siloxane portioncomprising a branched siloxane structure, and at least one hydrophilicorganopolymer portion which is linear or branched, where the percentagesby weight are based on the total weight of a) and b).
 24. Thesilicone-containing polymer of claim 23, wherein a branched polysiloxaneb) comprises structural elements of the formulaY[—C_(n)H_(2n)—(_(R2SiO))_(m)-A_(p)-R₂Si-G]_(x) (I), where Y is atrivalent to decavalent hydrocarbon radical optionally containing one ormore heteroatoms selected from the group consisting of oxygen, nitrogenand silicon atoms, radicals R are identical or different monovalent,optionally halogenated C₁₋₁₈ hydrocarbon radicals, A is a radical of theformula —R₂Si—R¹—(R₂SiO)_(m)—, where R¹ is a divalent C₂₋₃₀ hydrocarbonradical, the carbon atoms of which are optionally interrupted by one ormore nonadjacent oxygen atoms, G is a monovalent radical of the formula—C_(n)H_(2n)-Z or —C_(n)H_(2n−2k)-Z, or a divalent radical—C_(n)H_(2n)—where the second bond in the divalent radical is to a further radical Y,Z is a monovalent hydrophilic radical, x is an integer from 3 to 10, kis 0 or 1, n is an integer from 1 to 12, m is an integer of at least 1,and p is 0 or a positive integer, with the proviso that the branchedpolysiloxanes have on average at least one group Z and the group Zcontains at least one oxygen atom or nitrogen atom.
 25. Thesilicone-containing polymer of claim 24, wherein Y is a trivalent ortetravalent radical; A is a radical wherein R¹ contains from 1 to 4nonadjacent oxygen atoms; x is 3 or 4; n is 2; m is an integer from 1 to1000; and p is 0 or an integer from 1 to
 20. 26. The silicone-containingpolymer as claimed in claim 23, characterized in that at least oneradical Y is selected from radicals of the group consisting of


27. The silicone-containing polymer of claim 23, wherein the radical Zcomprises a hydrophilic building block in monomeric, oligomeric orpolymeric form, and whose solubility in water under standard conditionsis ≧1 g/l.
 28. The silicone-containing polymer of claim 27, wherein atleast one radical Z is a hydrophilic polymer selected from the groupconsisting of polyols, polyethers, polyacids and salts thereof,polyesters, polyureas, polycarbonates, and copolymers prepared from(meth)acrylic ester monomers and further copolymerizable comonomersbearing at least one carboxyl, amide, sulfonate, dialkylammonium, ortrialkylammonium functional group.
 29. The silicone-containing polymerof claim 28, wherein at least one radical Z comprises a homocondensateor cocondensate containing at least one alkylene oxide selected from thegroup consisting of ethylene oxide and propylene oxide.
 30. Thesilicone-containing polymer of claim 27, wherein at least one radical Zcontains a monomeric or polymeric radical bearing a hydrophilic radicalselected from the group consisting of hydroxyl groups, carboxyl groupsand salts thereof, sulfonic acid groups and salts thereof, sulfategroups, ammonium groups, keto groups, ether groups, ester groups, andamide groups.
 31. The silicone-containing polymer of claim 27, whereinat least one radical Z contains a radical selected from the groupconsisting of —(CH₂)₁₋₆—O—CH₂—CHOH—CH₂—SO₃—Na⁺,—(CH₂)₁₋₆—O—CH₂—CHOH—CH₂—N⁺(CH₃)₂CH₂CO₂ ⁻, —(CH₂)₁₋₆-(EO)₁₀₋₂₀—O—CH₃,—(CH₂)₁₋₆—O—SO₃—H₃N⁺—CH(CH₃)₂, —(CH₂)₁₋₆—N⁺(CH₃)₂—(CH₂)₁₋₆—SO₃—,—(CH₂)₁₋₆—O-(EO)₁₀₋₂₀—H, —(CH₂)₁₋₆—CHOH—CH₂—N⁺(CH₃)₂CH₂CO₂ ⁻, and—(CH₂)₁₋₆—CHOH—CH₂—N⁺(CH₃)₂—CH(CH₃)CH₂—CO₂ ⁻.
 32. Thesilicone-containing polymer of claim 23, wherein one or more silanesselected from the group consisting ofγ-acryloxypropyltri(alkoxy)silanes, andγ-methacryloxypropyltri(alkoxy)silanes,ω-methacryloxymethyltri(alkoxy)silanes,γ-methacryloxypropylmethyldi(alkoxy)silanes, vinylalkyldi(alkoxy)silanesand vinyltri(alkoxy)silanes are additionally copolymerized with themonomers a).
 33. The silicone-containing polymer of claim 23, whereinone or more epoxy-functional monomers selected from the group consistingof glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether andvinyl glycidyl ether are additionally copolymerized with the monomersa).
 34. The silicone-containing polymer of claim 23, wherein one or moresilicone macromers bearing at least one unsaturated group, and selectedfrom the group consisting of linear or branched polydi(C₁₋₆alkyl)-siloxanes with a chain length of from 10 to 1000SiO(C_(n)H_(2n+1))₂ units and which contain one or two terminal and/orinternal polymerizable groups are additionally copolymerized with themonomers a).
 35. A process for preparing a silicone-containing polymerof claim 23, comprising emulsion polymerizing polymerizable monomerscomprising a) from 60 to 99.99% by weight of at least one monomerselected from the group consisting of vinyl esters of unbranched orbranched C₁₋₁₅ alkylcarboxylic acids, methacrylic esters and acrylicesters of C₁₋₁₅ alcohols, vinylaromatics, monoolefins, dienes, and vinylhalides, in the presence of b) from 0.01 to 40% by weight of at leastone branched polysiloxane having lipophilic and hydrophilic portions, atleast one lipophilic siloxane portion comprising a branched siloxanestructure, and at least one hydrophilic organopolymer portion which islinear or branched, where the percentages by weight are based on thetotal weight of a) and b), and optionally drying a resulting polymerdispersion to a polymer powder.
 36. In a paint or coating compositionwherein a silicone-containing polymer is employed, the improvementcomprising selecting as at least one silicone-containing polymer, asilicone-containing polymer of claim
 23. 37. In a paint or coatingcomposition wherein a silicone-containing polymer is employed, theimprovement comprising selecting as at least one silicone-containingpolymer, a silicone-containing polymer of claim
 24. 38. The compositionof claim 36 which is an adhesive, silicate-rich paint, carbonate-richpaint, protective coating, release coating, or render.
 39. A cosmeticformulation comprising at last one silicone-containing polymer of claim23, and at least one further cosmetically acceptable ingredient.
 40. Thecosmetic formulation of claim 39 which is a hair care formulation.